Zinc Isotope Fractionation as an Indicator of Geochemical Attenuation Processes

Veeramani, Harish; Eagling, Jane; Jamieson-Hanes, Julia H.; Kong, Lingyi; Ptacek, Carol J.; Blowes, David W.

doi:10.1021/acs.estlett.5b00273

Cited by 51 publications

(45 citation statements)

References 67 publications

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“…The isotopic enrichment of hydrozincite is consistent with a positive theoretical fractionation factor calculated between this phase and aqueous Zn. This is also in agreement with the experimental work of Veeramani et al (2015). It should be noted that calculated β-factors values are for perfect minerals assuming stoichiometric Zn sites.…”

Section: Geochemical Implications For Natural Samplessupporting

confidence: 91%

“…Veeramani et al (2015) studied Zn isotope fractionation between aqueous solutions and minerals such as sphalerite, hydrozincite and hopeite, which is a Zn phosphate. Sphalerite and hydrozincite were precipitated from ZnSO 4 and ZnCl 2 solutions respectively, to which Na 2 S 2 and NaHCO 3 with varying concentration, were added in batch experiments, respectively.…”

Section: Comparison Between Theoretical and Experimentalmentioning

confidence: 99%

“…Furthermore, in experiments, the outer-sphere complex is undistinguishable in vibrational spectroscopy investigations from the bulk phase sulfate (Rudolph et al, 1999). As a consequence of these observations, we assume that the fractionation measured in Veeramani et al (2015) experiments could be roughly approximated to represent isotopic fractionation between minerals and Zn(H 2 O) 2+ 6 complex. The value ε = −0.30 (respectively ε = +0.18 ) would represent thus an average fractionation factor between sphalerite (respectively hydrozincite) and Zn hexaaquo complex.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…Gélabert et al (2006) and John et al (2007) Weiss et al (2005Weiss et al ( , 2007, Viers et al (2007), Moynier et al (2009b) and Aucour et al (2011) have found roots to be enriched in heavy isotopes with respect to leaves and shoots. Studies by Pokrovsky et al (2005), Balistrieri et al (2008), Juillot et al (2008), Bryan et al (2015) and Veeramani et al (2015) investigated isotopic fractionation induced by adsorption on oxides and hydroxides and have reported a preferential sorption of heavy isotopes on minerals surface. Guinoiseau et al (2016) measured enrichment in heavy isotopes at phyllosilicates surface with ∆ 66 Zn adsorbed-solution ranging from 0.11 at low pH and low ionic strength to 0.49 at high pH and high ionic strength.…”

Section: Introductionmentioning

confidence: 99%

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Equilibrium zinc isotope fractionation in Zn-bearing minerals from first-principles calculations

2016

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Isotopic composition analysis contributes significantly to the investigation of the biogeochemical cycle of zinc with its economical, environmental and health implications. Interpretation of isotopic measurements is however hindered by the lack of a set of equilibrium isotopic fractionation factors between Zn-bearing minerals. In this study, equilibrium mass-dependent Zn isotope fractionation factors in Zn-bearing minerals are determined from first-principles calculations within the density functional theory (DFT) scheme. A wide range of minerals belonging to sulfide, carbonate, oxide, silicate, sulfate and arsenate mineral groups are modelled to account for the natural diversity of Zn crystal-chemical environment. Calculated reduced partition function ratios (β-factors) span a range smaller than 2 at 22 • C. All studied secondary minerals (adamite, gahnite, gunningite, hemimorphite, hydrozincite, zincite) but zinc carbonate (smithsonite) are isotopically heavier than zinc sulfide minerals (sphalerite and wurtzite) from which they could form through supergene processes. Zinc-aluminium spinel and zinc silicate are the isotopically heaviest minerals. The investigation of the crystalchemical parameters at the origin of differences in isotopic properties shows an excellent linear correlation between ln β and Zn interatomic force constants. β-factors are also observed to increase when the Zn-first neighbour bond lengths decrease and charges on atoms involved in the bonding increase and vice versa. These findings are in line with the observation of heavy isotope enrichment in systems having the largest bond strength.

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Section: Geochemical Implications For Natural Samplessupporting

confidence: 91%

Section: Comparison Between Theoretical and Experimentalmentioning

confidence: 99%

Section: Accepted Manuscriptmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Equilibrium zinc isotope fractionation in Zn-bearing minerals from first-principles calculations

2016

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“…±0.07‰ and +0.53 ±0.07 ‰ (Balistrieri et al, 2009;Juillot et al, 2008), other studies have shown that the light isotopes likely became enriched in the sulfidic phases Kelley et al, 2009;Veeramani et al, 2015). Therefore, it is plausible that the cycling of zinc within sedimentary mangrove environments, coupled to well-known intense redox reactions, experience significant isotopic fractionation.…”

Section: Accepted M Manuscriptmentioning

confidence: 96%

Tracing of anthropogenic zinc sources in coastal environments using stable isotope composition

et al. 2017

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The use of zinc isotopes to trace anthropogenic sources in coastal areas has been tested in this study. We determined the stable isotopic composition of zinc in sediment cores, suspended particulate matter (SPM) and rocks collected at the Sepetiba Bay (southeastern Brazil), an estuarine lagoon heavily impacted by metallurgic activities.These isotopic signatures were compared with those from willemite ore, which represent the main mineral refined by the major industrial source of zinc. The aim was to test if this tracer system enables to identify sources and sinks of anthropogenic zinc and to reconstruct the temporal and spatial evolution of zinc contamination. can be useful to improve environmental monitoring efforts in coastal systems.

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The Potential of Zn Isotopes in the Science and Exploration of Ore Deposits

Wilkinson

2023

Mineral Resource Reviews

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Since the turn of the Century, the growth in development and application of zinc isotopes to multiple fields in terrestrial and planetary sciences has been exponential. The potential for the application of zinc isotope systematics to ore deposit formation processes was obvious from the outset, given that they represent the most significant concentrations of zinc on Earth and because this approach allowed, for the first time, direct assessment of zinc metal origins and transport. This contribution presents a brief summary of the notation and analytical procedures for analysis of zinc isotopes and summarizes the terrestrial data reported to date. These results show that the variation in zinc isotope composition in rocks and ore systems is in fact rather small (< 2 ‰), linked, at least in part, to the single oxidation state in which zinc occurs in nature. Based on an assessment of the literature, the principal mechanisms for causing isotopic fractionation are all relatively low temperature processes: (i) biogenic; (ii) supergene dissolution-reprecipitation; (iii) adsorption–desorption reactions; and (iv) hydrothermal precipitation. High temperature igneous processes do not appear to produce significant isotopic variations. In ore deposit studies, it currently appears unlikely that zinc isotopes can be used to constrain potential metal sources, apart from zinc derived from carbonate host rocks which tends to be isotopically heavy. However, there are a number of systems in which systematic variation in δ66Zn of sulfides suggests that Rayleigh-type fractionation during ore mineral precipitation occurs, opening up the possibility of using zinc isotopes to trace flow paths and vector in towards mineralized centers. Modeling of such hydrothermal processes is currently hindered by a paucity of experimentally-determined fractionation factors, but as such work is done, our ability to better understand and utilize zinc isotopic zonation patterns for the purposes of mineral exploration will be progressively enhanced.

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Zinc Isotope Fractionation as an Indicator of Geochemical Attenuation Processes

Abstract: 17Isotope ratio measurements have been used to trace environmental processes, especially in subsurface 18 environments. In this study we evaluated the potential to use Zinc (Zn)

Cited by 51 publications

References 67 publications

Equilibrium zinc isotope fractionation in Zn-bearing minerals from first-principles calculations

Equilibrium zinc isotope fractionation in Zn-bearing minerals from first-principles calculations

Tracing of anthropogenic zinc sources in coastal environments using stable isotope composition

The Potential of Zn Isotopes in the Science and Exploration of Ore Deposits

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